CN105198004B - A kind of Fe3O4‑SnO2Nano composite material and preparation method thereof - Google Patents
A kind of Fe3O4‑SnO2Nano composite material and preparation method thereof Download PDFInfo
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- CN105198004B CN105198004B CN201510507166.7A CN201510507166A CN105198004B CN 105198004 B CN105198004 B CN 105198004B CN 201510507166 A CN201510507166 A CN 201510507166A CN 105198004 B CN105198004 B CN 105198004B
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Abstract
The invention discloses a kind of Fe3O4‑SnO2Nano composite material and preparation method thereof, including Fe3O4Microsphere and it is coated on Fe3O4SnO outside microsphere2Nanometer rods, described Fe3O4A diameter of 200～500nm, SnO of microsphere2Nanometer rods are along Fe3O4Microsphere spherical radius direction arrangement cladding, SnO2The draw ratio of nanometer rods is 4～10；Fe is prepared by solvent-thermal method mainly3O4Magnetic microsphere, then in Fe3O4Pass through Hydrothermal Growth SnO on magnetic microsphere2Monocrystal nano rod；Without the need for any template and catalyst in water-heat process, process is simple, yield are high and with low cost, are adapted to batch production；Fe3O4Microsphere directly coats growth SnO as core2Nanometer rods, prepared monocrystalline SnO2Nanometer rods form is homogeneous, in Fe3O4It is evenly coated on microsphere.
Description
Technical field
The invention belongs to field of nanometer material technology, is related to a kind of Fe3O4-SnO2Nano composite material and preparation method thereof.
Background technology
The development of modern science and technology, undoubtedly needs more outstanding material to support.Nowadays, multi-level, various dimensions, multicomponent
Hierarchy design and synthesis be expected to solve people's demand growing to new material, substantial amounts of hierarchy by
Conception has even had been applied in solaode, optoelectronic device, lithium ion battery negative material, hydrogen storage material, radar wave and has inhaled
Receive the numerous areas such as material, photocatalysis, biosensor, biodegradation, biological medicine.But, research at this stage is limited to
Synthesis technique at this stage and technology, it is urgently to be resolved hurrily still to there are a series of bottleneck problems in the material of hierarchy, is such as difficult to close
It is single etc. into, simple structure, species, therefore people urgently find a kind of simply and easily method to prepare the material of hierarchy
Material.People are devoted to the preparation of various hierarchies, such as ZnO hierarchies, CuO-ZnO hierarchies, Fe always for many years3O4-
TiO2Classification mechanism, ZnO-SnO2Deng.
SnO2It is a kind of typical N-shaped direct band gap broad stopband oxide semiconductor material, it has the following aspects
Advantage：(1) there is broad-band gap (Eg=3.6eV) and high exciton bind energy (130meV) under room temperature；(2) low cost；(3) prepare
Method and product form various structures.The above feature causes SnO2Have which only in semiconductor device and field of functional materials
Special advantage and broad application potential, especially SnO2Low-dimension nano material is in catalyst, the negative pole of lithium ion battery
The aspects such as material, electro-magnetic wave absorption, solaode, sensor, opto-electronic device show wide application prospect.So
And, Fe3O4It is a kind of important magnetic Nano material, due to its distinctive magnetic property, has had been applied in numerous areas, such as
The application of the aspects such as microwave absorption, biosensor, sewage disposal, pharmaceutical carrier, enzyme are fixed, biosensor；By two
Person is combined into a nanometer hierarchy, SnO2Excellent semiconducting behavior and Fe3O4Magnetic property is organically blended, and will make them
Application expand significantly, or even at present, had substantial amounts of research worker to be devoted to studying Fe3O4- metal-oxide
Nanostructured simultaneously obtains related achievement, and such as Chinese patent CN103157430A discloses a kind of Hemicentrotus seu Strongylocentrotuss shape core-shell type Fe3O4@
TiO2Magnetic microsphere and its preparation and application, the material have good practical value and application prospect in fields such as protein sciences.
Although having formed Hemicentrotus seu Strongylocentrotuss shape nucleocapsid structure, its preparation process is loaded down with trivial details, needs first to prepare Seed Layer using sol-gal process laggard
Water-filling thermal response, and yield rate is low.
The content of the invention
For defect of the prior art and deficiency, the invention provides one kind is directly in Fe3O4SnO is coated on microsphere2Receive
The preparation method of rice rod composite construction, solves the problems, such as that preparation process is loaded down with trivial details and yield rate is low.
To solve above-mentioned technical problem, the technical scheme that the present invention takes is：
A kind of Fe3O4-SnO2Nano composite material, including Fe3O4Microsphere and it is grown in Fe3O4SnO on microsphere2Nanometer rods.
Specifically, including monomer, described monomer includes Fe3O4Microsphere and it is grown in Fe3O4SnO on microsphere2Nanometer rods.
Specifically, described Fe3O4A diameter of 200～500nm, SnO of microsphere2Nanometer rods are along Fe3O4Microsphere spherical radius
Direction arrangement cladding, SnO2The draw ratio of nanometer rods is 4～10.
More specifically, described SnO2A diameter of 30～50nm, SnO of nanometer rods2The length of nanometer rods be 200～
300nm。
Prepare described Fe3O4-SnO2The method of nano composite material, prepares Fe including using solvent-thermal method3O4Microsphere, then
In Fe3O4Hydrothermal Growth SnO is adopted on microsphere2Nanometer rods.
Specifically, described solvent-thermal method prepares Fe3O4Microsphere includes：Iron containing compoundses, chelating agent and surfactant three
Solvent thermal reaction is carried out at 200 DEG C after the dissolving of person's mixed diluting, the product of reaction is washed to neutral post-drying and obtains final product Fe3O4It is micro-
Ball.
More specifically, described iron containing compoundses are FeCl3, FeCl3Concentration after dilution dissolving is 0.1～0.3mol/L,
Described surfactant be PEG20000, PEG20000 dilution dissolving after concentration be 0.0001～
0.003mol/L, described chelating agent are CH3COONa, CH3Concentration after COONa dilution dissolvings is 0.5～0.7mol/L.
Further, the solvent of iron containing compoundses, chelating agent and surfactant three's mixed diluting is ethylene glycol.
In addition, described in Fe3O4Hydrothermal Growth SnO is adopted on microsphere2Nanometer rods include：By Fe3O4Microsphere, stanniferousization
After compound, the dissolving of surfactant mixed diluting, then toward mixed solution, add highly basic as reaction source at 160～210 DEG C
8～24h of insulation carries out hydro-thermal reaction, and the product washing of reaction is neutral and drying Fe3O4-SnO2Nano composite material.
Meanwhile, Fe3O4The concentration of microsphere is 0.1～0.3mol/L, and described sn-containing compound is SnCl4, SnCl4It is dense
Spend for 0.05～0.3mol/L, described highly basic is NaOH, NaOH and SnCl4Molar concentration rate be [NaOH]:[SnCl4]=9
～15:1.
Advantages of the present invention is：
(1) the Hemicentrotus seu Strongylocentrotuss shape Fe that the present invention is prepared3O4-SnO2Nano composite material is in a diameter of 200～500nm
Fe3O4Microsphere surface is coated with SnO2Monocrystal nano rod, and SnO2The common centre of sphere of monocrystal nano rod is along Fe3O4Magnetic microsphere radial direction
Arrangement, SnO2A diameter of 30～50nm of nanometer rods, its length are 200～300nm, and its draw ratio is 4～10；From microstructure
On see, Hemicentrotus seu Strongylocentrotuss shape Fe3O4-SnO2Nucleocapsid structure has very big specific surface area, can serve as gas sensor；From hierarchy
Physical property fusion on see, Hemicentrotus seu Strongylocentrotuss shape Fe3O4-SnO2Nano composite material both should have good absorption energy to radar wave magnetic component
Power, also has good absorbability to radar wave electric component, is a kind of excellent absorbing material；
(2) present invention is preparing Fe3O4-SnO2During nano composite material, using hydro-thermal method in Fe3O4Microsphere surface grows
SnO2Monocrystal nano rod, without the need for any template and catalyst in water-heat process, process is simple, yield are high and with low cost, are adapted to
Batch production；
(3)Fe3O4Microsphere directly coats growth SnO as core2Nanometer rods, prepared monocrystalline SnO2Nanometer rods form is homogeneous,
In Fe3O4It is evenly coated on microsphere.
Description of the drawings
Fig. 1 is the X ray diffracting spectrum of embodiment 1 in the present invention；
Fig. 2 is the XRD spectrum of embodiment 2 in the present invention；
Fig. 3 is the XRD spectrum of embodiment 3 in the present invention；
Electron scanning micrographs of the Fig. 4 for embodiment 1；
SEM photographs of the Fig. 5 for embodiment 2；
SEM photographs of the Fig. 6 for embodiment 3；
Fig. 7 is the Fe of the present invention3O4-SnO2SnO in nano composite material2The typical SEAD photo of nanometer rods；
The present invention is illustrated below in conjunction with specification drawings and specific embodiments.
Specific embodiment
Fe prepared by the present invention3O4-SnO2Nano composite material shape such as Hemicentrotus seu Strongylocentrotuss, are with Fe3O4Magnetic microsphere be core, with
SnO2Monocrystal nano rod be hull shape into complex, homogeneous quadrangular shape SnO2The common centre of sphere of monocrystal nano rod is along Fe3O4Magnetic is micro-
The evenly distributed structure in radius of a ball direction.
It is of the invention mainly to adopt solvent-thermal method and hydro-thermal method, by controlling the concentration of pink salt in reaction system, alkali salt ratio, anti-
The factors such as temperature, response time are answered to obtain a kind of Hemicentrotus seu Strongylocentrotuss shape Fe3O4-SnO2Nano composite material and the method for preparing the material,
Without the need for any template and catalyst in water-heat process, process is simple, yield are high and with low cost, are adapted to batch production；Fe3O4It is micro-
Ball directly coats growth SnO as core2Nanometer rods, prepared monocrystalline SnO2Nanometer rods form is homogeneous, in Fe3O4Coat on microsphere
Uniformly.
Fig. 7 is product Hemicentrotus seu Strongylocentrotuss shape Fe of the present invention3O4-SnO2" shell " (SnO in nano composite material2Nano wire) constituency electricity
Sub- diffraction images, the diffraction spot on photo disclose the SnO2Nano wire is monocrystalline.
In order that objects and advantages of the present invention become more apparent, the present invention is carried out below in conjunction with drawings and Examples
Further describe.It should be appreciated that specific embodiment described herein is not used to limit only to explain the present invention
The present invention.
Embodiment one：
With FeCl3·6H2O、CH3COONa·3H2The mixture of O and PEG10000 is solute, with ethylene glycol as solvent, is filled
Divide stirring, obtain the FeCl of 0.2mol/L3·6H2The CH of O, 0.65mol/L3COONa·3H2O's and 0.00286mol/L
The ethylene glycol mixed solution of PEG10000, takes out 35mL ethylene glycol mixed solution immigration teflon-lined reactor (interior
The volume of lining is 50ml) in, be sealed against being placed in 200 DEG C of baking ovens and be incubated 8h, question response terminate after by product carry out from
Heart separating treatment, and, until the pH=7 of filtrate, then products therefrom is placed in 60 DEG C in baking oven with absolute ethanol washing repeatedly
Lower drying, just obtains Fe3O4Microsphere；By Fe3O4Microsphere, SnCl4·5H2The mixture of O and PEG10000 adds appropriate deionization
Water is sufficiently stirred for, Fe in gained mixed solution3O4Microsphere is 0.1mol/L, SnCl4·5H2O is 0.05mol/L, and PEG10000 is
0.001mol/L, by mixed solution supersound process 15 minutes after, 0.45mol/L NaOH solutions are dropwise added dropwise to into above-mentioned mixing
It is ultrasonic 15 minutes again after solution, precursor solution is just obtained, 35ml precursor solutions has been taken out and is moved into polytetrafluoroethyllining lining
Reactor (volume of liner be 50ml) in, 8h is incubated in being sealed against being placed in 160 DEG C of baking ovens, question response will be anti-after terminating
Answer product to be centrifuged, and be washed with deionized repeatedly, until the pH=7 of filtrate, products therefrom is placed in into baking then
Dry at 60 DEG C in case, just obtain Hemicentrotus seu Strongylocentrotuss shape Fe3O4-SnO2Nano composite material.The X ray diffracting spectrum of the product such as Fig. 1 institutes
Show, electron scanning micrograph is as shown in Figure 4；
The product of Fig. 1 explanation embodiments one is Fe3O4-SnO2Complex, the product of Fig. 4 explanation embodiments one have Hemicentrotus seu Strongylocentrotuss
Shape Fe3O4-SnO2Nucleocapsid structure pattern.
Embodiment two：
With FeCl3·6H2O、CH3COONa·3H2The mixture of O and PEG10000 is solute, with ethylene glycol as solvent, is filled
Divide stirring, obtain the FeCl of 0.2mol/L3·6H2The CH of O, 0.65mol/L3COONa·3H2O's and 0.00286mol/L
The ethylene glycol mixed solution of PEG10000, takes out 35mL ethylene glycol mixed solution immigration teflon-lined reactor (interior
The volume of lining is 50ml) in, be sealed against being placed in 200 DEG C of baking ovens and be incubated 8h, question response terminate after by product carry out from
Heart separating treatment, and, until the pH=7 of filtrate, then products therefrom is placed in 60 DEG C in baking oven with absolute ethanol washing repeatedly
Lower drying, just obtains Fe3O4Microsphere；By Fe3O4Microsphere, SnCl4·5H2The mixture of O and PEG10000 adds appropriate deionization
Water is sufficiently stirred for, Fe in gained mixed solution3O4Microsphere is 0.2mol/L, SnCl4·5H2O is 0.15mol/L, and PEG10000 is
0.002mol/L, by mixed solution supersound process 15 minutes after, 1.5mol/L NaOH solutions are dropwise added dropwise to into above-mentioned mixing molten
It is ultrasonic 15 minutes again after liquid, precursor solution is just obtained, 35ml precursor solutions has been taken out and is moved into teflon-lined
In reactor (volume of liner is 50ml), 16h in being sealed against being placed in 200 DEG C of baking ovens, is incubated, question response will be anti-after terminating
Answer product to be centrifuged, and be washed with deionized repeatedly, until the pH=7 of filtrate, products therefrom is placed in into baking then
Dry at 60 DEG C in case, just obtain Hemicentrotus seu Strongylocentrotuss shape Fe3O4-SnO2Nano composite material.The X ray diffracting spectrum of the product such as Fig. 2 institutes
Show, electron scanning micrograph is as shown in Figure 5；
Fig. 2 explanation two products of embodiment are Fe3O4-SnO2Complex, the product of Fig. 5 explanation embodiments two have Hemicentrotus seu Strongylocentrotuss shape
Fe3O4-SnO2Nucleocapsid structure pattern.
Embodiment three
With FeCl3·6H2O、CH3COONa·3H2The mixture of O and PEG10000 is solute, with ethylene glycol as solvent, is filled
Divide stirring, obtain the FeCl of 0.2mol/L3·6H2The CH of O, 0.65mol/L3COONa·3H2O's and 0.00286mol/L
The ethylene glycol mixed solution of PEG10000, takes out 35mL ethylene glycol mixed solution immigration teflon-lined reactor (interior
The volume of lining is 50ml) in, be sealed against being placed in 200 DEG C of baking ovens and be incubated 8h, question response terminate after by product carry out from
Heart separating treatment, and, until the pH=7 of filtrate, then products therefrom is placed in 60 DEG C in baking oven with absolute ethanol washing repeatedly
Lower drying, just obtains Fe3O4Microsphere；By Fe3O4Microsphere, SnCl4·5H2The mixture of O and PEG10000 adds appropriate deionization
Water is sufficiently stirred for, Fe in gained mixed solution3O4Microsphere is 0.3mol/L, SnCl4·5H2O is 0.3mol/L, and PEG10000 is
0.003mol/L, by mixed solution supersound process 15 minutes after, 4.5mol/L NaOH solutions are dropwise added dropwise to into above-mentioned mixing molten
It is ultrasonic 15 minutes again after liquid, precursor solution is just obtained, 35ml precursor solutions has been taken out and is moved into teflon-lined
In reactor (volume of liner is 50ml), 24h in being sealed against being placed in 210 DEG C of baking ovens, is incubated, question response will be anti-after terminating
Answer product to be centrifuged, and be washed with deionized repeatedly, until the pH=7 of filtrate, products therefrom is placed in into baking then
Dry at 60 DEG C in case, just obtain Hemicentrotus seu Strongylocentrotuss shape Fe3O4-SnO2Nano composite material.The X ray diffracting spectrum of the product such as Fig. 3 institutes
Show, electron scanning micrograph is as shown in Figure 6；
The product of Fig. 3 explanation embodiments three is Fe3O4-SnO2Complex, the product of Fig. 6 explanation embodiments three have Hemicentrotus seu Strongylocentrotuss
Shape Fe3O4-SnO2Nucleocapsid structure pattern.
In sum, the present invention relates to a kind of Hemicentrotus seu Strongylocentrotuss shape Fe3O4-SnO2The preparation method of nanostructured composites, is adopted
Solvent thermal and hydro-thermal preparation process process is simple, controllability is strong, and yield is high, with low cost, is adapted to batch production.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (3)
1. a kind of Fe3O4-SnO2Nano composite material, it is characterised in that including Fe3O4Microsphere and it is grown in Fe3O4On microsphere
SnO2Nanometer rods；
Described Fe3O4A diameter of 200～500nm, SnO of microsphere2Nanometer rods are along Fe3O4Microsphere spherical radius direction arrangement bag
Cover, SnO2The draw ratio of nanometer rods is 4～10；
Described SnO2A diameter of 30～50nm, SnO of nanometer rods2The length of nanometer rods is 200～300nm.
2. Fe as claimed in claim 13O4-SnO2Nano composite material, it is characterised in that including monomer, described monomer bag
Include Fe3O4Microsphere and it is grown in Fe3O4SnO on microsphere2Nanometer rods.
3. the Fe described in claim 1 or 2 is prepared3O4-SnO2The method of nano composite material, it is characterised in that include using molten
Agent full-boiled process prepares Fe3O4Microsphere, then in Fe3O4Hydrothermal Growth SnO is adopted on microsphere2Nanometer rods；
Described solvent-thermal method prepares Fe3O4Microsphere includes：Iron containing compoundses, chelating agent and surfactant three's mixed diluting
Solvent thermal reaction is carried out after dissolving at 200 DEG C, the product of reaction is washed to neutral post-drying and obtains final product Fe3O4Microsphere；
Described iron containing compoundses are FeCl3, FeCl3Concentration after dilution dissolving is 0.1～0.3mol/L, and described surface is lived
Property agent be PEG20000, PEG20000 dilution dissolving after concentration be 0.0001～0.003mol/L, it is described
Chelating agent is CH3COONa, CH3Concentration after COONa dilution dissolvings is 0.5～0.7mol/L；
The solvent of iron containing compoundses, chelating agent and surfactant three's mixed diluting is ethylene glycol；
It is described in Fe3O4Hydrothermal Growth SnO is adopted on microsphere2Nanometer rods include：By Fe3O4Microsphere, sn-containing compound, surface
After the dissolving of activating agent mixed diluting, then toward mixed solution, add highly basic that 8～24h is incubated at 160～210 DEG C as reaction source
Hydro-thermal reaction is carried out, the product washing of reaction is neutral and drying Fe3O4-SnO2Nano composite material；
Fe3O4The concentration of microsphere is 0.1～0.3mol/L, and described sn-containing compound is SnCl4, SnCl4Concentration be 0.05～
0.3mol/L, described highly basic are NaOH, NaOH and SnCl4Molar concentration rate be [NaOH]:[SnCl4]=9～15:1.
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| CN105914358B (en) * | 2016-06-24 | 2018-03-13 | 扬州大学 | The preparation method of yolk eggshell structure nitrogen-doped carbon coated ferriferrous oxide@tin ash magnetic Nano boxes |
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